Novel adsorbent

ABSTRACT

An adsorbent is disclosed which is formed either by coating an adsorption mass such as active carbon with a gel-like substance such as the dibasic metallic salt of a macromolecular polycarboxylic acid, soybean curd, jelly, konjak, agar, perilla, gelidium jelly, or chitosanoxalic acid salt gel and subsequently subjecting the coated basis to a freezing treatment or by effecting the coating with the gel-like substance already made to contain a frost damage preventing substance such as glycerin and subsequently depriving the coated basis of the frost damage preventing substance. This adsorbent, on being brought into direct contact with foodstuffs or ingested directly into the digestive system, effects highly efficient removal by adsorption of such food additive, feed additive, agricultural pesticide, food poisoning substance, allergen, heavy metal or highly poisonous organic compound as are suffered to adhere to or exist in the foodstuffs, such surplus nutrients as persist in the digestive system, such oligomers and additives as are contained in liquors, such metabolites of alcohol as are formed in the digestive system after assimilation of alcohol, such harmful substances as hydroperoxides of unsaturated fatty acids as are suffered to exist in oils and fats, and such components of offensive odor as emanate from fish.

TECHNICAL FIELD

[0001] This invention relates to a novel adsorbent to be used in agentsfor the removal of harmful substances by adsorption. More particularly,the invention relates to an adsorbent which is formed by coating anadsorption basis with a gel-like substance.

BACKGROUND ART

[0002] The active carbon possesses a large specific surface area andexhibits a great ability to effect adsorption and finds utility as arepresentative adsorbent in various applications. When the active carbonis directly ingested into the digestive system as a medicinal carbon forthe purpose of removing by adsorption such substances as induceautointoxication, medicinal poisoning, etc. however, it is liable to doharm by causing constipation. When an effort is made to mingle theactive carbon with a foodstuff and ingest the mixture into the digestivesystem, it is at a disadvantage in imparting an unpleasant sensation tothe palate and smearing the foodstuff in a blackish tint. It is alsoknown that in the animal cell, the active carbon in a finely dividedstate is adsorbed on the protein or sugar protein in the outer layer ofthe cell membrane. When the active carbon in the finely divided state isdirectly ingested into the digestive system as an agent for the removalof a harmful substance by adsorption, it is suspected that part thereofpersists in a state adsorbed on the cells in the digestive system withfastness such that thorough elimination thereof from the digestivesystem may be extremely difficult.

[0003] With a view to solving this problem, adsorbents formed by coatingactive carbon with water-insoluble mannan such as konjak or with across-linked polymer such as calcium alginate have been proposed(JP-A-55-95,611 and JP-A-04-210,239). Since these adsorbents result fromforming a surface coat on the particles of active carbon, they sufferfrom such problems as inducing a decrease in the surface area andimpeding ample manifestation of the ability of adsorption inherent inthe active carbon.

[0004] This invention has been created in the light of the problemencountered by the prior art as described above. It has for an objectthereof the provision of an adsorbent which keeps intact the ability ofadsorption inherent in the adsorption basis such as of active carbonand, on being brought into direct contact with foodstuffs or ingesteddirectly into the digestive system, effects highly efficiently theremoval by adsorption of such harmful substances as are suffered toadhere to or mingle into the foodstuffs or suffered to occur in thedigestive system.

DISCLOSURE OF THE INVENTION

[0005] The object mentioned above is accomplished by this inventionproviding an adsorbent which is formed by coating an adsorption basiswith a gel-like substance and subsequently subjecting the coated basisto a freezing treatment.

[0006] The object is further accomplished by this invention providing anadsorbent which is formed by coating an adsorption basis with a gel-likesubstance already containing a frost damage preventing substance andsubsequently depriving the coated basis partly or wholly of the frostdamage preventing substance.

[0007] This invention further concerns the adsorbent, wherein the frostdamage preventing substance mentioned above is glycerin.

[0008] This invention further concerns the adsorbent, wherein theadsorption basis mentioned above is a carbonaceous material possessingthe ability to effect adsorption.

[0009] This invention further concerns the adsorbent, wherein thecarbonaceous material possessing the ability to effect adsorption isactive carbon or charcoal.

[0010] This invention further concerns the adsorbent, wherein thegel-like substance mentioned above is the divalent metallic salt of amacromolecular polycarboxylic acid.

[0011] This invention further concerns the adsorbent, wherein thedivalent metallic salt of the macromolecular polycarboxylic acidmentioned above is calcium alginate.

[0012] This invention further concerns the adsorbent, wherein thegel-like substance mentioned above is soybean curd, jelly, konjak, agar,perilla, gelidium jelly, or chitosanoxalic acid salt gel.

[0013] This invention further concerns the adsorbent which is formed bydrying the adsorbent mentioned above.

[0014] This invention further concerns the adsorbent which comprises anadsorbent moiety formed by coating an adsorption basis with a firstgel-like substance and a second gel-like substance moiety.

[0015] This invention further concerns the adsorbent which is formed byseasoning either the adsorbent moiety mentioned above or the secondgel-like substance moiety mentioned above.

[0016] This invention further concerns the adsorbent wherein theadsorbent moiety mentioned above comprises any of the adsorbentsmentioned above.

[0017] This invention further concerns an agent for the removal byadsorption of a harmful substance, which agent comprises any of theadsorbents mentioned above.

[0018] This invention further concerns an agent for removal byadsorption of a harmful substance, wherein the harmful substancementioned above is a food additive, a feed additive, an agriculturalpesticide, a food poisoning substance, allergen, a heavy metal, or astrongly poisonous organic compound which is suffered to adhere to ormingle in a foodstuff or an animal feed or assimilated into thedigestive system.

[0019] This invention further concerns the agent mentioned above forremoval by adsorption of a harmful substance, wherein the feed additivementioned above is an antibiotic substance, a synthetic antibacterialagent, or a hormone.

[0020] This invention further concerns the agent mentioned above forremoval by adsorption of the harmful substance, wherein the foodpoisoning substance mentioned above is exotoxins, autotoxins, or aharmful chemical substance.

[0021] This invention further concerns the agent for removal byadsorption of a harmful substance, wherein the agent mentioned above isformed of the adsorbent mentioned above and the harmful substancementioned above is formed of an antibiotic substance which has eitherundergone oral ingestion or acted on the intestinal bacteria.

[0022] This invention further concerns the agent for removal byadsorption of a surplus nutrient assimilated in the digestive system,wherein the agent mentioned above is formed of the adsorbent mentionedabove.

[0023] This invention further concerns the agent for removal byadsorption of the metabolite of alcohol formed in the digestive systemin consequence of the assimilation of the alcohol, wherein the agentmentioned above is formed of the adsorbent mentioned above.

[0024] This invention further concerns the agent for removal byadsorption of the hydroperoxide of an unsaturated fatty acid, whereinthe agent mentioned above is the adsorbent mentioned above.

[0025] This invention further concerns a deodorant formed of theadsorbent mentioned above.

[0026] This invention further concerns a processed foodstuff or animalfeed incorporating therein the adsorbent mentioned above in an amount inthe range of 0.01-6 wt. %.

[0027] This invention further concerns the processed foodstuff mentionedabove which is a dairy product, a product of fish paste, a processedfish or shellfish, a processed meat, processed beans, processedvegetables, a processed potato, a processed cereal, a sweetener, oil andfat, or a cake.

[0028] It is considered that when the adsorbent of this invention isformed by coating an adsorption basis with a gel-like substance and thensubjecting the coated basis to a freezing treatment, this adsorbent isenabled to keep intact the ability to effect adsorption possessedinherently by the adsorption basis because the moisture in the gel-likesubstance forming the coat is coagulated and is consequently allowed toform in the coat such minute pores as have a larger diameter than thepores which would be formed solely by cross-linkage.

[0029] It is considered that when the adsorbent is formed by coating theadsorption basis with the gel-like substance already containing a frostpreventing substance and then depriving the coated basis of the frostpreventing substance, this adsorbent is enabled to manifest the sameeffect as mentioned above because the procedure so employed producessimilar minute pores in the gel-like substance forming the coat.

[0030] When the adsorbent of this invention uses minute particles ofpowdered active carbon, for example, as the adsorption basis, it assumesthe constitution of a dispersion system having the adsorption basisuniformed dispersed in the gel-like substance. The adsorbent, therefore,permits highly efficient removal by adsorption of a harmful substancebecause the adsorbent in its entirety enjoys an increase in the surfacearea available for adsorption and a consequent increase in the abilityto effect adsorption as compared with the adsorbent produced by solelyusing active carbon in a highly dispersed state.

[0031] Since the adsorbent of this invention has the adsorption basiscoated with the gel-like substance, it can be directly ingested into thedigestive system and utilized therein for effecting ready removal byadsorption of a harmful substance which has mingled in a foodstuff andconsequently succumbed to assimilation therein. The adsorbent, on beingdirectly ingested into the digestive system, does not induce suchadverse effects as constipation. The adsorbent which has effected theremoval by adsorption of the harmful substance in the digestive systemcan be very quickly and easily discharged from the digestive system.

[0032] The adsorbent of this invention is only required to mingle intoor contact a foodstuff to implement the removal by adsorption of theharmful substance contained in the foodstuff. In this case, theadsorbent which has effected the removal of the harmful substance byadsorption can be separated easily and quickly from the foodstuff ascompared with the adsorbent which is used all by itself. Further, evenwhen the adsorbent escapes the separation and entrains the foodstuff andsuccumbs to assimilation in the digestive system, it warrants safetybecause it can be quickly discharged from the digestive system asmentioned above.

[0033] The adsorbent of this invention can be utilized by being mixedwith a processed foodstuff besides being directly ingested into thedigestive system as described above. When the adsorbent of thisinvention is mixed with the processed foodstuff and the resultantmixture is put to use for eating, it produces no sensation of thepresence of foreign particles, excels in palatability, and avoidspolluting the food material in a black tint.

[0034] The adsorbent of this invention can be utilized for animals beingraised besides being utilized for human beings as an agent for theremoval by adsorption of substances harmful to human beings. Theadsorbent of this invention can be utilized for treating animal feed orit can be utilized for directly feeding the animals or by being mixedwith the animal feed prepared for feeding the animals.

BEST MODE FOR CARRYING OUT THE INVENTION

[0035] The adsorbent of this invention can be obtained by coating anadsorption basis with a gel-like substance and subsequently subjectingthe coated basis to a freezing treatment.

[0036] As concrete examples of the adsorption basis to be used in theproduction of the adsorbent of this invention, active carbon, charcoal,alumina, silica gel, zeolite, bentonite, calcium phosphate, ion-exchangeresin, and chelating resin may be cited. Among other adsorption basesmentioned above, such carbonaceous materials as active carbon andcharcoal which possess the ability to effect adsorption prove favorable.The active carbon proves particularly suitable.

[0037] When the active carbon is used as the adsorbent, it can be usedin various forms such as, for example, powder, granules, and fibers. Itis nevertheless particularly favorable to use the active carbon in thepowdery or granular form. In this case, the active carbon is preferredto have a particle diameter in the range of 5 μ-10 mm. If the particlediameter of the active carbon is less than 5 μm. the active carbon willnot be handled easily. If the particle diameter exceeds 10 mm, theability of the active carbon to effect adsorption per unit weight willbe unduly low. The amount of the active carbon to be incorporated in thegel-like substance is preferred to be in the range of 0.02-90 wt. %. Ifthis amount of the active carbon is less than 0.02 wt. %, the activecarbon will not be sufficiently effective in attaining necessaryadsorption. If the amount exceeds 90 wt. %, the active carbon will bedispersed in the gel-like substance only with difficulty.

[0038] As the gel-like substance to be used in the adsorbent of thisinvention, the gel-like substance such as, for example, the divalentmetal salt of a macromolecular polycarboxylic acid which, when injectedinto the digestive system, does no harm may be cited. As concreteexamples of the divalent metal salt of a macromolecular polycarboxylicacid, calcium, magnesium, iron, and copper salts of such macromolecularcompounds as alginic acid, pectic acid, carboxymethyl cellulose,carboxymethyl chitin, styrene-maleic acid copper, styrene-maleic acidsemialkyl ester copolymer, ethylene-acrylic acid copolymer, polyacrylicacid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer,acrylic acid-maleic acid copolymer, and acrylic acid-maleic acidsemialkyl ester copolymer which possess a carboxyl group in the sidechain may be cited.

[0039] The adsorbent which uses the divalent metal salt of amacromolecular polycarboxylic acid is obtained by adding the suspensionof an alkali metal salt or an ammonium salt of a macromolecularpolycarboxylic acid and an adsorption basis such as, for example, activecarbon powder dropwise into an aqueous divalent metal salt solution. Theconcentration of the alkali metal salt or ammonium salt of themacromolecular polycarboxylic acid in the suspension mentioned above ispreferred to be in the range of 0.01-5 mols. If the concentration isless than the lower limit of the range, the gel thoroughly coating ordispersing the adsorption basis will not be obtained. If theconcentration exceeds the upper limit, the amount of the salt of themacromolecular carboxylic acid which surrounds the adsorption basis willbe so large as to impede the infiltration of a substance for adsorptioninto the adsorption basis and degrade conspicuously the ability of theadsorbent to effect necessary adsorption. The concentration of theaqueous divalent metal salt is preferred to be in the range of 0.05-5mols. If this concentration is less than the lower limit, the adsorptionbasis will have no sufficient strength because the ratio ofcross-linkage is unduly small. If it exceeds the upper limit, theinfiltration of the substance for adsorption into the adsorption basiswill be attained with difficulty because the ratio of cross-linkage isunduly large and the pores in the adsorption basis have an extremelysmall diameter.

[0040] The gel-like substances which can be used in this inventioninclude such gel-like foodstuffs as soybean curd, jelly, konjak, agar,perilla, and gelidium jelly and chitosanoxalic acid salt gel, forexample. The adsorbent which uses such a gel-like substance is obtainedby suitably adding and dispersing the adsorption basis such as, forexample, active carbon powder prior to the formation of gel during thecourse of production of the relevant gel-like foodstuff.

[0041] The adsorbent of this invention allows the gel-like substancesmentioned above to be used either singly or in the form of a mixture oftwo or more members. This adsorbent, as occasion demands, allowsaddition thereto of such viscosity enhancers as almond gum, AEROMONASUgum, ASOTOBAKUTAA, BINERANJII gum, AMASHIIDO gum, gum arabic,arabinogalactan, alginic acid, AROEBERA extract, UERAN gum, ERUWINIA,MITSUENSHISU gum, EREMI resin, ENTEROBAKUTAA.MITSUENSHISU gum,ENTEROBAKUTAA gum, ORAKU extract, KAADORAN, seaweed cellulose, KASHIAgum, brown seaweed extract, KARAGINAN, karaya gum, KAROBUBIIN gum,GACHII gum, xanthan gum, KITACHIAROE extract, chitin, chitosan, guayulegum, glucosamine, yeast cell membrane, SAIRYUMUSHIIDO gum, JURAN gum,SUKURERO gum, YASURERO gum, SESUBANIA gum, TAMARINDOSHIIDO gum, TARAgum, DANMARU resin, PUKISUTOSSO, tragacanth gum, TORIAKANSOSU gum,TOROROAOI, Bacillus natto gum, fibrillous cellulose, NOASERERAN,ZORURAN, pectin, MAKUROHOMOBUSHISU gum, RAMUZAN gum, and levan, such gumbases as ERENU resin, OURIKYURIROU, OZOKERAITO, NABOBANAKKUSU resin,KAURI gum, carnauba wax, KANDERIWOwax, whalewax, crown gum, guttaKACHU,gutta HANKAN, gutta BERUKA, guaiac resin, guayule, KOOPARU resin,KOPAIPAPARUSAMU, rice bran wax, rum, decomposed rubber resin, sugarcanewax, SANDARAKKU resin, Shellac (refined shellc and white shellac),shellc wax, JURUTON, SORUBA, SORUBINBA, talc, DAMMARU resin, CHIKUBURU,chicle, TSUMEE, low molecular rubber, NYUKOU, nigger gutta, NITSUBERO,balata, paraffin socks, fur balsam, powdered pulp, powdered rice hull,Venezuela chicle, benzoin gum, BERIIJO, HOHOBA wax, MASSARANDOBAchocolate, MASSARANDO BABARATA, microcrystalline socks, mastic, honeywax, myrrh, sumac wax, montan wax, oilcake seed wax, lanolin,RETCHUBUBAKA, ROJIKINHA, and rosin, such brighteners as OURIKYURI wax,carnauba wax, KANDERIRA wax, whale wax, coriander seed, saffron, pricklyash, perilla, SYAROTTO, JUNIBAA berry, ginger, cinnamon, star anise oil,spearmint, sage, SEBORII, celery seed, thyme, water pepper, onion,tarragon, chicory, CHAIBU, CHAABIRU, extracted powder spice, Chilepepper, dill, nutmeg, leek, garlic, scallion, parsley, peppermint,paprika, pistachio, FENUGU leek, FENNERU seed, horse raddish, MAAJORAN,umbrelliferous plant, Japanese ginger, mace, MESU, citron, lime, redpepper, lemon, rosemary, laurel, and horse raddish, such dairy productsas cheese, fresh cream, butter, powdered milk, whey, and condensed milk,such liquors as curano, Kirschwasser, sherry, refined sake, beer, wine,brandy, powdered sake, vermouth, rum, and liqueur, and alpha starch,alpha rice, sweetened bean paste, UURON tea, EROUTEROKOKKU extract,dried vegetable, agar, gluten, chlorella, powdered blood, powdered bloodplasma, koji mold, black tea, coffee, yeast, ginseng, cocoa, powderedrice, corn flour, wheat malt, collagen, powdered konjak, acetobacter,sake lees, jam, table salt, protein from refined fish meat, protein fromrefined flour, protein from refined soybean, gelatin, buckwheat flour,seed malt, chocolate, dextrin, starch, corn flour, Bacillus subtilis,sparingly digestible dextrin, lactobacillus, lactose, malt, maltextract, ham, bifidobacterium bifidum, bran, partially alpha starch,powdered potato, powdered yam, monascus, hemicellulose, ground tea,citrous pulp, powdered egg yolk, egg yolk oil, albumen, and green tea.

[0042] The adsorbent of this invention can be otherwise obtained bycoating an adsorption basis with a gel-like substance already containinga frost harm preventing substance and subsequently depriving the coatedbasis partly or wholly of the frost harm preventing substance.

[0043] As concrete examples of the frost harm preventing substance to beused in the adsorbent of this invention, acetamide, L-alanine, albumin,ammonium acetate, chloroform, choline, dextran, diethylene glycol,dimethyl acetamide, dimethyl formamide, dimethyl sulfone, dimethylsulfoxide, erythritol, ethanol, ethylene glycol, formamide, glucose,glycerin, glycine, hydroxy ethyl starch, inositol, lactose, magnesiumchloride, magnesium phosphate, maltose, mannitol, mannose, methanol,methyl acetamide, methyl formamide, methyl urea, monoacetin, phenol,polyethylene glycol, polyethylene oxide, polyoxyethylene, polyvinylpyrrolidone, L-proline, propionamide, propylene glycol, pyridine,N-oxide, resorcinol, ribitol, ribose, L-serine, sodiumbromide, sodiumchloride, sodium iodide, sodium nitrate, sodium nitrite, sodium sulfate,sorbitol, sucrose, polyethylene glycol, urea, L-valene, and xylose maybe cited. Among other frost harm preventing substances cited above,glycerin proves particularly advantageous.

[0044] Incidentally, when the adsorbent of this invention is utilized ina form proper for ingestion into the digestive system, the adsorbentitself may be properly seasoned for the purpose of facilitating theingestion.

[0045] The adsorbent of this invention can be used for the purpose ofremoving by adsorption such harmful substances as food additives, feedadditives, agricultural pesticides, food poisoning substances, allergen,heavy metals, and strongly poisonous organic compounds which have beenattached to or contained in food or feed or assimilated into thedigestive system.

[0046] Specifically, the adsorbent of this invention is usable for theremoval by adsorption of food additives represented by such sweetenersas saccharin and salts thereof, dipotassium glycyrrhizate, tripotassiumglycyrrhizate, and ethyl acetacetate, such coloring agents as ironsesquioxide, food dye red Nos. 3, 40, 102, 104, 105, and 106, food dyeyellow Nos. 4 and 5, food dye green No. 3, food dye blue Nos. 1 and 2,and titanium dioxide, such preserving agents as benzoic acid,orthophenyl phenol, sorbic acid, dehydroacetic acid, propionic acid andsalts thereof, diphenyl, thiapentazole, and paraoxybenzoic esters, suchquality preserving agents as propylene glycol, such viscosityenhancer-gelling agent-pasting agent as propylene glycol alginate,potassium carboxymethyl cellulose, sodium carboxymethyl cellulose,sodium starch glycolate, sodium starch phosphate, methyl cellulose, andpolysodium acrylate, such antioxidants as dl-α-tocopherol, sorbic acidand sodium salt thereof, guaiac resin, isopropyl citrate, dibuyl hydroxytoluene, nordihydro-guaiaretic acid, butylhydroxy anisole, propylgallate, calcium disodium ethylenediamine tetraacetate, and disodiumethylene-diamine tetraacetate, such color formers as sodium nitride,potassium nitrate, sodium nitrate, ferric sulfate, and phosphates, suchfungicidal agents as hydrogen peroxide, hypochlorous acid, and sodiumhypochlorite, such bleaching agents as sulfurous acid and salts thereof,and such antifungous and antibacterial agents as diphenyl andthiapentazole.

[0047] As respect agricultural pesticides, the adsorbent of thisinvention can be applied to the removal by adsorption of fungicides,insecticides, and herbicides using such organic phosphorus compounds asMEP, Diazinone, PAP, IBP, EDDP, DDVP, DEP, Marathione, and EPN, suchorganic chlorine compounds as Chlorosalonyl, Chloropycrin, D-D,Pyrazolate, PCNB, Flacide, DCIP, and Procimidone, such carbamates asBPMC, MTMC, XMC, MCC, and MIPC, such organic bromine compounds as methylbromide, such benzoimidazoles as Thiophanate Methyl, such thiocarbamatesas Penthiocurb, such diphenyl ethers as CNP, such chlorine compounds aschlorates, such phthalimides as Captan, such dithiocarbamates as Maneb,such bipyridiums as Paracoat, such diphenyl ethers as Chloromethoxynyl,such acid amides as DCPA, such copper compounds as inorganic coppercompounds, and such compounds as Sethoxydim, Isoprothioran, Propenazol,Dimuron, and Naproanilide. The other harmful substances that permiteffective use of the adsorbent of this invention for the removal byadsorption include such allergens as histamine which causes allergy-likefood poisoning and arises from the putrefaction of meat, for example,such heavy metals as mercury, lead, hexavalent chromium, cadmium,selenium, arsenic, copper, iron, and zinc, and such strongly poisonousorganic compounds as phosphides, chlorides, and benzene.

[0048] The adsorbent of this invention can be also utilized for theremoval by adsorption of exotoxins, autotoxins, and harmful chemicalsubstances which are food poisoning substances. As concrete examples ofthe exotoxins, toxins produced by intestine infecting bacteria such asbotulinum-producing toxins (types A-F), clostridium difficile-producingenterotoxin and cytotoxin, clostidium perfringens-producing enterotoxin,toxin protoza escherichia coli-producing readily heatable enterotoxinand thermoduric enterotoxin, dysentery-producing Shiga toxin,staphylococcus-producing enterpotoxins (types A-E), Vibriocholera-producing cholera toxin, vibrio parahaemolyticus-producingthermoduric hemolytic toxin and enterotoxin, and ersiniaentrochocolitica-producing enterotoxin, berotoxins produced by intestinehemorrhagic E. coli such as berotoxin, and celeus-producing toxin may becited. As concrete examples of the autotoxins, tetrodotoxin (toxin oftetraodontiformes), such mushroom toxins as amatoxins, phallotoxins,muscarine, muscaridine, ibotenic acid, bufotenine, muscimol, psilocybin,psilocin, serotinin, gyromitrin (helvellic acid), and illudin, suchparalytic shell toxins as succitoxin, neosuccinitoxin, and goniotoxin,such diarrheal shell toxins as dinophicis toxin-1,-3, and pectenotoxin,such toxins of fish and shellfish as vitamin A (poisoning of stripedjewfish), penelpin (poisoning of little neck clam), tetramine (poisoningof tetramine), neo-Suruga toxin and pro-Suruga toxin (poisoning of ivoryshell), and Pipheoholbyte a (sunlight dermatitis), solanin (potato),atropine, scopolamine, L-hyoscyamine, aconitine, hydrogen cyanide (whichexists in the form of a non-toxic hydrocyanic acid complex in the seedsof Japanese apricot, peach, apricot, apple, and pear and gives rise tohydrocyanic acid in the system), 4′-methoxy pyridoxin (poisoning ofginko), and aflatoxin (poisoning of mildew) may be cited. As concreteexamples of the harmful chemical substance, methanol, arsenic, cyancompounds, sodium glutamate, sodium saccharine, tin, copper, zinc,cadmium, arsenic compounds, and sodium fluoride may be cited.

[0049] Further, by the adsorbent of this invention, such harmfulsubstances as are formed by antibiotic substances which have been orallyinjected or by antibiotic substances which have acted on theenterobacteria can be removed.

[0050] In recent years, the practice of adding antibiotic substances andsynthetic antibacterial agents to the feed with a view to promoting thegrowth of domestic animals, treating the infectious diseases affectingthe animals, or preventing the animals from the diseases and thepractice of giving hormones such as estrigen to bulls with a view toimproving the quality of meat have been in vogue. The manifestation ofallergic symptoms and abnormal sexual growths and the development ofcarcinogenicity of synthetic antibacterial agents due to the consumptionof such diary products and meats as contain the ingested additives asresidues have come to pose a problem. The adsorbent of this inventioncan be further utilized for the removal by adsorption of such antibioticsubstances as penicillin which persist in diary products and meat, suchsynthetic antibacterial agents as sulfa drugs, and such feed additivesas hormones like progestron and estradiol.

[0051] The adsorbent of this invention can be used further for theremoval by adsorption of such surplus nutrients as have escapedassimilation in the digestive system. The adsorbent of this invention,in a test for the culture of cells, functions to inhibit the propagationof cells by adsorbing the sources of nutritions in the culture medium.When it is ingested together with hood before or after the meal, itrepresses the metabolism of the food, for example. It, therefore, can beutilized as an agent for resisting corpulence or for the purpose ofdietary cure. Specifically, by substituting the adsorbent of thisinvention for about 20% of the standard diet, the amount of thenutriment to be adsorbed is substantially lowered to 60-64% because theadsorbent of this invention further removes by adsorption 20-25% of thenutriment of the food. By repeating this substitution while payingattention to the loss of body weight, it is made possible to accomplishthe gradual loss of body weight and the ultimate correction of bodyweight to a proper level. Moreover, this dietary cure can be continuedfor a long time because the person practicing the dietary cure does notfeel hungry or stressful because the amount of the food to be consumeddoes not change from the standard level.

[0052] Further, the adsorbent of this invention can be used for removingby adsorption oligomers and additive substances which are contained inliquors and removing by adsorption acetaldehyde and other metabolites ofalcohol which are formed in the digestive system in consequence of theconsumption of liquors. Specifically, the metabolism of alcohol (ethylalcohol) in a mammal gradually advances and forms acetaldehyde as anintermediate metabolite, with the result that the acetaldehyde will besubsequently oxidized into acetic acid and acetyl-CoA. In thismetabolism of alcohol, the rise of the concentration of acetaldehydeultimately induces such symptoms as retch, nausea, facial flush, rise ofpulsation, headache accompanied by sudden pulsation, rise of cutaneoustemperature, and fall of minimum blood pressure (acetaldehyde symptoms,i.e. so-called hangover). The oligomers and additives which arecontained in liquors are also held responsible partly for the symptoms.By taking the adsorbent of this invention during, before, or after thecourse of drinking thereby removing by adsorption the oligomers andadditives contained in the liquors and consequently removing byadsorption the acetaldehyde formed in the digestive system, therefore,it is made possible to preclude or cure such acetaldehyde symptoms. Thesymptom of poisoning due to erroneous consumption of methanol issimilarly caused by the intermediate metabolite of alcohol. Theadsorbent of this invention can be utilized likewise for the cure ofacidosis.

[0053] The adsorbent of this invention can be also used for the removalby adsorption of functional oligomers having molecular weights of100-some tens of thousand such as, for example, such pathogenic proteinsas prion, fatty acids, saccharides, and compounds combining them.

[0054] Further, the adsorbent of this invention can be used on personscomplaining of medicinal poisoning caused by barbituric acid type drugs,agricultural pesticides, hypnotic drugs, sedative drugs, antidepressiondrugs, analgesic drugs, drugs for affecting cardiac blood vessels,antibiotic substances, anticancer drugs, and stimulants with a view toeffecting removal by adsorption of the relevant medicines.

[0055] The adsorbent of this invention can be used for the removal byadsorption of hydroperoxides of unsaturated fatty acids which areresponsible for the acid putrefaction of oils and fats such as, forexample, edible oils. The acid putrefaction of oils and fats such as,for example, edible oils is chiefly caused by the fact that theunsaturated fatty acids in the oils and fats are autoxidated by theoxygen in the air and consequently caused to form hydroperoxides. Thehydroperoxides are further decomposed to produce aldehydes, ketones, andlower fatty acids which have adverse effects on smell and taste. Theadsorbent of this invention can be utilized also as an agent forpreventing oils and fats from acid putrefaction because it is capable ofadsorbing such hydroperoxides of unsaturated fatty acids formed in oilsand fats by the autoxidation.

[0056] Further, the adsorbent of this invention can be used for theremoval by adsorption of offensive odors from fish. To be specific, theadsorbent of this invention can be utilized as a deodorant because itremoves by adsorption such volatile salts as ammonia and trimethylaminewhich are odorous components of fish, such volatile acids as diluteacids and acetic acid, such volatile carbonyl compounds as formaldehydeand acetaldehyde, such volatile sulfur-containing compounds as hydrogensulfide and methyl mercaptan, such non-carboxyl neutral compounds asalcohols and phenols, and other typical odorous components.

[0057] Another aspect of this invention resides in providing a processedfood or feed which incorporates the adsorbent therein in an amount inthe range of 0.01-60 wt. %. The amount of the adsorbent of thisinvention incorporated in the processed food, etc. is defined in therange of 0.01-60 wt. % because the processed food will not acquire asufficient ability to effect necessary adsorption if the amount is lessthan 0.01 wt. % and the processed food will fail to acquire necessarytexture and palatability for food and will suffer from serious sensationof the presence of foreign matter if the amount exceeds 60 wt. %.

[0058] As concrete examples of the processed food which permitsincorporation of the adsorbent, such dairy products as yogurt andcheese, such pastes of fish meat as kamaboko, chikuwa, hampen,satsumaage, naruto, and tsumire, such processed meats of fish andshellfish as dembu, such processed meats as sausages, frankfurters, andlever pastes, such leguminous products soybean curd, burnt soybean curd,fried soybean curd, deep-fried soybean curd, fried soybean curd cakewith stuffed ingredients, frozen soybean curd, and yuba, such processedvegetables as puree, processed potatoes such as mashed potato, arrowrootstarch, rice flour dumplings, boiled rice, rice vermicelli, macaroni,spaghetti, fine noodles, buckwheat noodles, noodles, chinese noodles,bread, biscuits, and sweetened bread cakes, such sweeteners as jam, suchoils and fats as butter, margarine, mayonnaise, and dressing, suchconfectioneries as candy, rakugan, rice biscuits, sponge cake,adzuki-bean paste, bean-jam wafers, buns filled with bean jam, softround rice cake stuffed with sweet bean jam, dumplings, uiro, chocolate,biscuits, cookies, doughnuts, cakes, pies, ice cream, budding, andBavarian cream, such gel-like foodstuffs as soybean curd, jelly, konjak,agar, perilla, and gelidium jelly, and such seaweeds as kelp, wakame,layer, and agar weed may be cited.

[0059] The incorporation of the adsorbent in a processed food such as,for example, jelly may be accomplished by a procedure which comprisesforming an unseasoned part (layer) and a seasoned part (layer) andincorporating the adsorbent in the unseasoned part (layer) or aprocedure which comprises incorporating into the unseasoned jelly theadsorbent which has been seasoned in advance as described above with aview to preventing the adsorbent from adsorbing the seasoned part of theprocessed food.

[0060] Now, this invention will be described more specifically belowwith reference to working examples. It should be noted, however, thatthis invention is not limited to these working examples.

EXAMPLE 1

[0061] Production of adsorbent (frozen active carbon-containing konjak)

[0062] In 750 ml of warm water kept at 30° C., a thorough mixture of 16g of refined flour and 4 g of active carbon having an average particlediameter of 15 μm was gently added piecemeal to the warm water lest itshould form small wet lumps and then stirred and heated with strong firefor about five minutes. After the heated mixture began to boil, it wascontinuouly stirred over medium fire for 7-8 minutes and thereaftercooled to about 40° C. A solution of 0.64 g of CaO thoroughly ground ina mortar in 50 ml of warm water kept at 40° C. was added to the cooledmixture. They were quickly kneaded together. The resultant blend wasplaced in a pattern box and pressed thoroughly therein with finger tipsto extract the entrapped air and homogenize the texture. The blend asheld in the pattern box was placed in a bath of hot water, heatedtherein for about five minutes, removed from the pattern box, andfurther heated in hot water for 25 minutes until thorough coagulation toobtain 640 g of active carbon-containing konjak.

[0063] The portion, 500 g, of the active carbon-containing konjakproduced as described above was placed in 1 liter of cold water, frozentherein at −30° C., left standing therein for five hours, then removedfrom the cold water, and thawed in hot water at 80° C. for one minute.The konjak was deprived of harshness by being left standing in a streamof water and cut into small dice, about 1 mm³ in volume, to obtain theadsorbent of this invention (frozen active carbon-containing konjak).

EXAMPLE 2

[0064] Production of adsorbent (frozen and dried activecarbon-containing konjak)

[0065] An adsorbent of this invention (frozen and dried activecarbon-containing konjak) was obtained by thoroughly drying 200 g of theadsorbent produced in Example 1 in a drier.

EXAMPLE 3

[0066] Production of adsorbent (glycerin-added active carbon-containingkonjak)

[0067] In 750 ml of an aqueous 5 wt. % glycerin solution kept at 30° C.,a thorough mixture of 16 g of refined flour and 16 g of active carbonhaving an average particle diameter of 30 m was gently added piecemealto the warm aqueous solution lest it should form small wet lumps andthen stirred and heated with strong fire for about five minutes. Afterthe heated mixture began to boil, it was continuouly stirred over mediumfire for 7-8 minutes and thereafter cooled to about 40° C. A solution of0.64 g of CaO thoroughly ground in a mortar in 50 ml of warm water keptat 40° C. was added to the cooled mixture. They were quickly kneadedtogether. The resultant blend was placed in a pattern box and pressedthoroughly therein with finger tips to extract the entrapped air andhomogenize the texture. The blend as held in the pattern box was placedin a bath of hot water, heated therein for about five minutes, removedfrom the pattern box, and further heated in 1000 ml of an aqueous 5 wt.% glycerin solution for 25 minutes until thorough coagulation to obtain650 g of glycerin-added active carbon-containing konjak. It was deprivedof glycerin and freed from harshness by being left standing in a streamof water and cut into small dice, about 1 mm³ in volume, to obtain theadsorbent of this invention (glycerin-added active carbon-containingkonjak).

EXAMPLE 4

[0068] Production of Adsorbent (glycerin-added frozen activecarbon-containing konjac)

[0069] The amount, 500 g, of the glycerin-added active carbon-containingkonjok produced by following the procedure of Example 3 was frozen inliquefied nitrogen (−196° C.) and then thawed in warm water kept at 40°C. The konjak was deprived of glycerin and freed from harshness by beingexposed to a stream of water and cut into dice, about 1 mm³ in volume,to obtain an adsorbent of this invention (glycerin-added, frozen, activecarbon-containing konjak).

EXAMPLE 5

[0070] Production of adsorbent (glycerin-added, dried, and activecarbon-containing konjak)

[0071] An adsorbent of this invention (glycerin-added, dried, and activecarbon-containing konjak) was obtained by further drying thoroughly 200g of the adsorbent produced in Example 3 in a drier.

EXAMPLE 6

[0072] Production of adsorbent (glycerin-added, frozen, dried, andactive carbon-containing konjak)

[0073] An adsorbent of this invention (glycerin-added, frozen, dried,and active carbon=-containing konjak) was obtained by further dryingthorough 200 g of the adsorbent produced in Example 4 in a drier.

[0074] [Control 1]

[0075] Production of adsorbent (active carbon-containing konjak)

[0076] An adsorbent for comparison (active carbon-containing konjak) wasobtained by following the procedure of Example 1 while omitting thefreezing and thawing treatments.

[0077] [Control 2]

[0078] Production of adsorbent (dried active carbon-containing konjak)

[0079] An adsorbent for comparison (dried active carbon-containingkonjak) was obtained by thoroughly drying 200 g of the adsorbentobtained in Control 1 in a drier.

EXAMPLE 7

[0080] Production of adsorbent (frozen active carbon-containing calciumalginate gel ball)

[0081] A thorough mixture of 2 g of sodium alginate and 3 g of activecarbon having an average particle diameter of 15 μm was added piecemealas kept stirred into 800 ml of cold water. The resultant mixture wasdiluted with added water to a total volume of 100 ml and stirred for 24hours to prepare a solution of sodium alginate containing 0.3 wt. % ofactive carbon. Separately, 11.1 g of calcium chloride was dissolved in800 ml of distilled water and the resultant solution was diluted withadded distilled water to a total amount of 1000 ml to prepare an aqueous1.11 wt. % calcium chloride solution.

[0082] Then, the sodium alginate solution was introduced into a buret,500 ml in volume, and added drop by drop into 500 ml of the calciumchloride solution mentioned above to obtain 10 g of crude gel balls ofactive carbon-containing calcium alginate. These crude gel balls wereplaced in a container, 5 liters in volume, and treated with a stream ofdeionized water for 10 hours to remove the unaltered reactants and theby-products and obtain gel balls of active carbon-containing calciumalginate.

[0083] Ten (10) g of the gel balls of active carbon-containing calciumalginate produced above were frozen at −85° C. and then thawed in hotwater at 40° C. The gel balls were deprived of the unaltered reactantsand the by-products by being exposed to a stream of water to produce anadsorbent of this invention (frozen gel balls of activecarbon-containing calcium alginate).

EXAMPLE 8

[0084] Production of adsorbent (gel balls of frozen, dried, and activecarbon-containing calcium alginate)

[0085] An adsorbent of this invention (gel balls of frozen, dried, andactive carbon-containing calcium alginate) was obtained by furtherdrying thoroughly 10 g of the adsorbent produced in Example 7 in adrier.

EXAMPLE 9

[0086] Production of adsorbent (gel balls of glycerin-added activecarbon-containing calcium alginate)

[0087] A thorough mixture of 2 g of sodium alginate and 3 g of activecarbon having an average particle diameter of 15 μm was added piecemealas kept stirred into 800 ml of an aqueous 5 wt. % glycerin solution. Theresultant mixture was diluted with added water to a total amount of 1000ml and stirred for 24 hours to prepare a glycerin solution of sodiumalginate containing 0.3 wt. % of active carbon. Separately, a solutionof 11.1 g of calcium chloride in 800 ml of distilled water was dilutedwith added distilled water to a total amount of 1000 ml to obtain anaqueous 1.11 wt. % calcium chloride solution.

[0088] Then, the glycerin solution of sodium alginate mentioned abovewas poured into a buret, 50 ml in volume, and added drop by drop into500 ml of the calcium chloride solution mentioned above to obtain 10 gof crude gel balls of glycerin-added active carbon-containing calciumalginate. The gel balls were placed in a container, 5 liters in volume,and deprived of the unaltered reactants and the by-products by beingexposed to a stream of deionized water to obtain an adsorbent of thisinvention (gel balls of glycerin-added active carbon-containing calciumalginate).

EXAMPLE 10

[0089] Production of adsorbent (gal balls of glycerin-added, frozen, andactive carbon-containing calcium alginate)

[0090] The amount, 10 g, of the adsorbent produced in Example 9 wasfrozen at −85° C. and then thawed in hot water kept at 40° C. Theadsorbent was deprived of the unaltered reactants and the by-products bybeing exposed to a stream of water to obtain an adsorbent of thisinvention (gel balls of glycerin-added, frozen, and activecarbon-containing calcium alginate).

EXAMPLE 11

[0091] Production of adsorbent (gel balls of glycerin-added, dried, andactive carbon-containing calcium alginate)

[0092] An adsorbent of this invention (gel balls of glycerin-added,dried, and active-carbon-containing calcium alginate) was obtained bythoroughly drying 10 g of the adsorbent produced in Example 9 in adrier.

EXAMPLE 12

[0093] Production of adsorbent (gel balls of glycerin-added, frozen, andactive carbon-containing calcium alginate)

[0094] An adsorbent of this invention) gel balls of glycerin-added,frozen, dried, and active carbon-containing calcium alginate) wasobtained by thoroughly drying 10 g of the adsorbent produced in Example10 in a drier.

[0095] [Control 3]

[0096] Production of adsorbent (gel balls of active carbon-containingcalcium alginate)

[0097] An adsorbent for comparison (gel balls of activecarbon-containing calcium alginate) was obtained by following theprocedure of Example 7 while omitting the freezing and thawingtreatments.

[0098] [Control 4]

[0099] Production of adsorbent (gel balls of dried activecarbon-containing calcium alginate)

[0100] An adsorbent for comparison (gel balls of dried and activecarbon-containing calcium alginate) was obtained by thoroughly drying 10g of the adsorbent produced in Control 3 in a drier.

EXAMPLE 13

[0101] Test for evaluation of speed of adsorption

[0102] The adsorbents produced in Examples 1-12 and Controls 1-4 weretested for the ability to effect adsorption by measuring their speeds ofadsorption.

[0103] In a 300-ml beaker, a 1-g sample weighed out of the relevantadsorbent was placed and made to add 50 ml of a dilute blue ink solution(0.112 in absorbance). The dilute ink solution, as kept stirred with thesample, was measured at intervals along the course of time for theabsorbance at a wavelength of 475 nm to find as the speed of adsorptionthe duration between the time the ink solution was added and the timethe adsorbance fell below 0.01. The results are shown in Table 1. Theconditions under which the adsorbents were treated are additionallyshown in the table.

[0104] Table 1

[0105] Adsorbent: Gel-like substance: Freezing treatment (Yes/No):

[0106] Drying treatment (Yes/No): Addition of glycerin (Yes/No):

[0107] Speed of adsorption (in minute)

[0108] Example 1—Konjak

[0109] Example 7—Calcium alginate gel

EXAMPLE 14

[0110] Test for removal of coloring material [food dye red No. 104(Floxin)] by adsorption

[0111] The coloring materials allowed for addition to food are used forthe purpose of beautifying the food or imitating the tint of naturalcolor of the food. In the synthetic tar type dyes, only suchwater-soluble dyes as the food dye red No. 104 are allowed at presentfor use in food. Their use is restricted.

[0112] The adsorbents produced in Example 3 and Control 1 were testedfor removal by adsorption of the food dye red No. 104 used in sausage.Twenty (20) g of sausage was finely ground. The ground sausage and 0.5 gof a given adsorbent and 100 ml of water added thereto were keptstirred. Liquid layers collected meanwhile in a fixed volume of 10 ml atintervals of a fixed length along the course of time were each dissolvedin five times its volume of hot water and then centrifuged. Thesupernatants consequently obtained were used as test solutions. The testsolutions were treated by the method described at pages 146-149 of the“Pictorial Guide to Method for Testing Food Hygiene” compiled by MisaoHaruta et al. and published by Chuo Hoki Press, with necessarymodifications, and rated for efficiency of removal by the filter paperchromatography.

[0113] The time which elapsed until the detection of the food dye redNo. 104 ceased to exist was one minute in the case of the adsorbent ofExample 3, whereas it was 10 minutes in the case of the adsorbent ofControl 1.

EXAMPLE 15

[0114] Test for removal of preservative [orthophenyl phenol (OPP)] byadsorption

[0115] Orthophenyl phenol shows clear signs of carcinogenicity andteratogenesis similarly to Thiambendazol (TBZ). This preservative iseffective in inhibiting the growth of fungi and various species ofaerobic and anaerobic bacteria and used in a wide variety of processedfoodstuffs.

[0116] The adsorbents produced in Example 10 and Control 3 were testedfor removal by adsorption of orthophenyl phenol in orange. In a beaker,50 g of a sample obtained by finely cutting orange was placed. Thesample and about 100 ml of water and one g of a given adsorbent addedthereto were kept stirred.

[0117] Liquid layers collected meanwhile in a fixed volume of 10 ml atintervals of a fixed length along the course of time were used as testsolutions. The test solutions were treated by the method described atpages 142-143 of the “Pictorial Guide to Method for Testing FoodHygiene” compiled by Misao Haruta et al. and published by Chuo HokiPress, with necessary modifications, and tested for orthophenyl phenolconcentration.

[0118] The time which elapsed until the orthophenyl phenol concentrationfell below the limit of detection (0.01 ppm) was three minutes in thecase of the adsorbent of Example 10, whereas it was 10 minutes in thecase of the adsorbent of Control 3.

EXAMPLE 16

[0119] Test for removal of antioxidant [dibutyl hydroxy toluene (BHT)]by adsorption

[0120] The antioxidant is effective in preventing loss of texture,keeping the nutritive value of food from being degraded by oxidation,preventing the processed fishery product from being sunburned, andpreventing a dye from being browned besides protecting oils and fatsagainst putrefaction by acid. It is used in a rich variety offoodstuffs.

[0121] The adsorbents produced in Example 10 and Control 3 were testedfor removal of dibutyl hydroxy toluene by adsorption in chewing gum. Ina 500-ml eggplant-shaped flask connected to a continuous extractorfitted with a reflux condenser, 5 g of chewing gum, 50 g of NaCl, 0.2 gof pyrogallol, 200 ml of water, boiling tips, and 1 g of a givenadsorbent were subjected to continuous extraction. Meanwhile, 10-mlextracted solutions were collected at intervals of a fixed length andused as test solutions. The test solutions were treated by the methoddescribed at pages 158-159 of the “Pictorial Guide to Method for TestingFood Hygiene” compiled by Misao Haruta et al. and published by Chuo HokiPress, with necessary modifications, and tested by the gaschromatography for dibutyl hydroxy toluene.

[0122] The time which elapsed until the dibutyl hydroxy tolueneconcentration fell below the limit of detection (0.01 g/kg) was fourminutes in the case of the adsorbent of Example 10, whereas it was 10minutes in the case of the adsorbent of Control 3.

EXAMPLE 17

[0123] Test for removal of fungicide (hydrogen peroxide) by adsorption

[0124] Hydrogen peroxide possesses a powerful oxidizing action and afungicidal power. The use of this fungicide has been banned since theoral ingestion thereof to mice was recognized to induce a cancer growth,though feebly, in the duodenum. At present, it is used only on herringroe.

[0125] The adsorbents produced in Example 3 and Control 1 were adoptedand tested for removal by adsorption of hydrogen peroxide in herringroe. About 5 g of finely cut herring roe was placed in an attriting cupand then stirred vigorously for 3 minutes with 40 ml of an exudingsolution added thereto, with the cup ice cooled externally. Theresultant mixture and 0.3 g of a given adsorbent added thereto were keptstirred. Liquid layers were collected meanwhile in a fixed volume of 10ml at intervals of a fixed length along the course of time. They weredeprived of bubbles formed therein by the addition of 0.1 ml ofsilicone, diluted with added water to a total amount of 50 ml, and thenthoroughly stirred and filtered. The filtrates, with the first 5-mlfractions thereof discarded, were used without any modification as testsolutions. These test solutions were treated by the method described atpages 144-145 of the “Pictorial Guide to Method for Testing FoodHygiene” compiled by Misao Haruta et al. and published by Chuo HokiPress, with necessary modifications, and tested for hydrogen peroxideconcentration by the measurement of oxygen potential.

[0126] The time which elapsed until the hydrogen peroxide concentrationfell below the limit of detection (0.01 ppm) was one minute in the caseof the adsorbent of Example 3, whereas it was five minutes in the caseof the adsorbent of Control 1.

EXAMPLE 18

[0127] Test for removal of bleaching agent (sulfurous acid) byadsorption

[0128] Sulfurous acid and salts thereof are effective not only inbleaching food but also in preserving food and preventing food fromoxidation and, therefore, are used as additives for numerous foodstuffs.Depending on the sort of foodstuff, their use is restricted with theamount of residual sulfur dioxide as a criterion.

[0129] The adsorbents produced in Example 1 and Control 1 were adoptedand tested for removal by adsorption of sulfuric acid in dried gourdshavings. The amount, 0.2 g, of finely sliced dried gourd shavings werekept stirred with 0.2 g of a given adsorbent and 20 ml of distilledwater added thereto. Liquid layers collected meanwhile in a fixed volumeof 10 ml at intervals of a fixed length along the course of time wereused as test solutions. These test solutions were treated by the methoddescribed at pages 150-151 of the “Pictorial Guide to Method for TestingFood Hygiene” compiled by Misao Haruta et al. and published by Chuo HokiPress, with necessary modifications, and tested for sulfurous acidconcentration by the modified Rankine method.

[0130] The time which elapsed until the sulfurous acid concentrationfell below the limit of detection (160 ppm) was five minutes in the caseof the adsorbent of Example 1, whereas it was ten minutes in the case ofthe adsorbent of Control 1.

EXAMPLE 19

[0131] Test for removal of female hormone (Estradiol) by adsorption

[0132] The adsorbents produced in Example 3 and Control 1 were adoptedand tested for removal by adsorption of Estradiol in beef. A 25-g sampletaken from the meat of a bull which had consumed a feed incorporatingEstradiol therein was increased to a total weight of 50 g by addingwater. The sample plus the water and 7 g of a given adsorbent were keptstirred. Liquid layers were collected meanwhile in a fixed volume of 10ml at intervals of a fixed length along the course of time andcentrifuged at 5000 rpm. The supernatants consequently formed wereadopted as test solutions. These test solutions were tested forEstradiol concentration in accordance with the method ofradioimmunoassay (RIA) [page 818 in the 30th revised edition of the“Glossary of Clinical Test Methods” compiled by Masamitsu Kanai andpublished by Kanahara Publishing K.K.] using an Estradiol testing kit(Estradiol=antibody kit made by Nippon DPC K.K.).

[0133] The time which elapsed until the Estradiol concentration fellbelow the limit of detection (5 pg/ml) was 1.5 minutes in the case ofthe adsorbent of Example 3, whereas it was ten minutes in the case ofthe adsorbent of Control 1.

EXAMPLE 20

[0134] Test for removal by adsorption of female hormone (Estradiol) inmilk

[0135] The adsorbents produced in Example 3 and Control 1 were adoptedand tested for removal by adsorption of Estradiol in milk. A stainlesssteel column measuring 3 mm in thickness, 6 cm in inside diameter, and100 cm in length was packed with lumps of a given adsorbent (5 mm×3mm×1.5 mm) to manufacture a column for removal by adsorption. Into thiscolumn, 5 liters of raw milk (fat ratio 3.0%) containing 300 pg/ml ofEstradiol was introduced at a flow speed of 2.8 liters/minute. Thetreated milk eluted from the column was collected in a fixed fraction of30 g at intervals of a fixed length along the course of time. Thesefractions and 150 g of H₂O added thereto were stirred for 30 minutes andcentrifuged at 10000 rpm. The supernatants obtained consequently wereused as samples. These samples were tested for Estradiol concentrationin the same manner as in Example 19. The time which elapsed until theEstradiol concentration fell below the limit of detection (5 pg/ml) wasthree minutes in the case of the adsorbent of Example 3, whereas it was30 minutes in the case of the adsorbent of Control 1.

EXAMPLE 21

[0136] Test for removal by adsorption of organic phosphur agent(Diazinone)

[0137] To date, 35 kinds of organic phosphorus agents have beenregistered as insecticides, 3 kinds thereof as fungicides, and 8 kindsthereof as herbicides. On account of low residue and low toxicity, theyhave found extensive utility.

[0138] The adsorbents produced in Example 9 and Control 3 were adoptedand tested for removal by adsorption of Diazinone in apples. A 20-gsample of slices of apple was placed in 100 ml of acetone and intimatelymixed by the use of a high-speed homogenizer for five minutes. Theresultant mixture and 1 g of a given adsorbent added thereto were keptstirred. Liquid layers were collected meanwhile in a fixed volume of 10ml at intervals of a fixed length along the course of time, filteredwith a funnel made by Kiriyama K.K. (filter aid 5 mm), and furthersubjected to extraction filtration with 100 ml of 30% hydrated acetone.The filtrates consequently obtained were used as test solutions. Thesetest solutions were treated by the method described at pages 94-95 ofthe “Pictorial Guide to Method for Testing Food Hygiene” compiled byMisao Haruta et al. and published by Chuo Hoki Press, with necessarymodifications, and tested by the gas chromatography for Diazinoneconcentration.

[0139] The time which elapsed until the Diazinone concentration fellbelow the limit of detection (10 ppb) was three minutes in the case ofthe adsorbent of Example 9, whereas it was five minutes in the case ofthe adsorbent of Control 3.

EXAMPLE 22

[0140] Test for removal by adsorption of organic chlorine agent[Chlorosalonyl (TPN)]

[0141] Since organic chlorine agents pose the problems of toxicity andresidue, their use has been banned to date nearly completely. OnlyChlorosalonyl (TPN), PCNB, phthalimidetype agents, Chlorobenzylates,etc. are still used today as fungicides and miticides.

[0142] The adsorbents produced in Example 10 and Control 3 were adoptedand tested for removal by adsorption of Chlorosalonyl in cucumbers. A20-g sample of slices of cucumber was placed in 100 ml of acetone andintimately mixed by the use of a high-speed homogenizer for fiveminutes. The resultant mixture and 1 g of a given adsorbent addedthereto were kept stirred. Liquid layers were collected meanwhile in afixed volume of 10 ml at intervals of a fixed length along the course oftime and subjected to extraction. The extracts consequently obtainedwere used as test solutions. These test solutions were treated by themethod described at pages 94-95 of the “Pictorial Guide to Method forTesting Food Hygiene” compiled by Misao Haruta et al. and published byChuo Hoki Press, with necessary modifications, and tested by the gaschromatography for Chlorosalonyl concentration.

[0143] The time which elapsed until the Chlorosalonyl concentration fellbelow the limit of detection (0.001 ppm) was three minutes in the caseof the adsorbent of Example 10, whereas it was ten minutes in the caseof the adsorbent of Control 3.

EXAMPLE 23

[0144] Test for removal by adsorption of carbamate agent

[0145] To date, 11 kinds of carbamate agents have been registered asinsecticides and 8 kinds thereof as herbicides. On account of lowtoxicity and low residue, they find extensive utility as insecticidessimilarly to the organic phosphorus agents.

[0146] The adsorbents produced in Example 3 and Control 1 were adoptedand tested for removal by adsorption of a carbamate agent in tomatos. A20-g sample of slices of tomato was placed in 100 ml of acetone andintimately mixed by the use of a high-speed homogenizer for fiveminutes. The resultant mixture and 1 g of a given adsorbent addedthereto were kept stirred. Liquid layers were collected meanwhile in afixed volume of 10 ml at intervals of a fixed length along the course oftime and subjected to extraction. The extracts consequently obtainedwere used as test solutions. These test solutions were treated by themethod described at pages 102-103 of the “Pictorial Guide to Method forTesting Food Hygiene” compiled by Misao Haruta et al. and published byChuo Hoki Press, with necessary modifications, and tested by the gaschromatography for carbamate agent concentration.

[0147] The time which elapsed until the carbamate agent concentrationfell below the limit of detection (0.001 ppm) was one minute in the caseof the adsorbent of Example 3, whereas it was ten minutes in the case ofthe adsorbent of Control 1.

EXAMPLE 24

[0148] Test for removal by adsorption of autotoxin (Solanine)

[0149] Solanine is an alkaloid glycoside which is present in the partsof new buds of potato. The LD₅₀ of this compound, when orally ingestedto a rabbit, is 0.45 g/kg. In human beings, it causes poisoning at aconcentration of 0.2-0.4 g.

[0150] The adsorbents produced in Example 9 and Control 3 were adoptedand tested for removal by adsorption of solanine in potato. A 5-g sampleof slices of potato was placed in 30 ml of methanol and intimately mixedby the use of a homogenizer for five minutes. The resultant mixture and0.5 g of a given adsorbent added thereto were kept stirred. Liquidlayers were collected meanwhile in a fixed volume of 10 ml at intervalsof a fixed length along the course of time and subjected to extraction.The extracts consequently obtained were used as test solutions. Thesetest solutions were treated by the method described at pages 82-83 ofthe “Pictorial Guide to Method for Testing Food Hygiene” compiled byMisao Haruta et al. and published by Chuo Hoki Press, with necessarymodifications, and tested by the liquid chromatography for solanineconcentration.

[0151] The time which elapsed until the solanine concentration fellbelow the limit of detection (0.001 ppm) was one minute in the case ofthe adsorbent of Example 9, whereas it was five minutes in the case ofthe adsorbent of Control 3.

EXAMPLE 25

[0152] Test for removal by adsorption of histamine

[0153] Such fishes of red flesh as mackerel, horse mackerel, and saurywhich tend to cause such food poisoning as allergy have high freehistidine contents in their muscles. When these fishes are contaminatedwith bacteria of strong histidine decarboxylase activity and weakhistaminase activity, they suffer accumulation of histamine.

[0154] The adsorbents produced in Example 1 and Control 1 were adoptedand tested for removal by adsorption of histamine in mackerel. A 10-gsample of muscles of mackerel was placed in 15 ml of water andhomogenizer for five minutes. The resultant mixture and one g of a givenadsorbent added thereto were kept stirred. Liquid layers were collectedmeanwhile in a fixed volume of 10 ml at intervals of a fixed lengthalong the course of time and adopted as test solutions. These testsolutions were treated by the method described at pages 134-135 of the“Pictorial Guide to Method for Testing Food Hygiene” compiled by MisaoHaruta et al. and published by Chuo Hoki Press, with necessarymodifications, and tested by the liquid chromatography for histamineconcentration.

[0155] The time which elapsed until the histamine concentration fellbelow the limit of detection (2.5 mg/100 g) was seven minutes in thecase of the adsorbent of Example 1, whereas it was ten minutes in thecase of the adsorbent of Control 1.

EXAMPLE 26

[0156] Test for removal by adsorption of cadmium

[0157] Cadmium is widely distributed in the natural world and used inlarge quantities on a commercial scale. The pollution of the environmentby the cadmium so used copiously in the industry and the contaminationof human organisms by the cadmium through the medium of foodstuffs havebecome a subject of discussion. Cadmium, when orally ingested in a largeamount, induces an acute gastrointestinal trouble and, when ingested ina minute amount, induces a renal trouble. The daily intake of cadmium bythe Japanese roughly averages 30-60 μg. It is estimated that 30-40% ofthe average originates in rice.

[0158] The adsorbents produced in Example 4 and Control 1 were adoptedand tested for removal by adsorption of cadmium in unpolished rice. In areaction vessel, 10 g of finely ground unpolished rice, 3 g of a givenadsorbent, 40 ml of distilled water, and sulfuric acid were placedsequentially in the order mentioned and were gradually heated together.When the liquid product of decomposition assumed a light yellow cleartexture, it was cooled and diluted with distilled water to a totalvolume of 100 ml. The dilute liquid was adopted as a test solution. Thistest solution was treated by the method described at pages 126-127 ofthe “Pictorial Guide to Method for Testing Food Hygiene” compiled byMisao Haruta et al. and published by Chuo Hoki Press, with necessarymodifications, and tested by the atomic adsorptiometric method forcadmium concentration.

[0159] The time which elapsed until the cadmium concentration fell belowthe limit of detection (0.02 ppm) was three minutes in the case of theadsorbent of Example 4, whereas it was ten minutes in the case of theadsorbent of Control 1.

EXAMPLE 27

[0160] Test for removal by adsorption of diethylene glycol (DEG)

[0161] Diethylene Glycol (DEG) is used as a solvent for the automobileantifreezing solution, brake oil compound, cellophane softener, andrubber oil and fat. The toxicity LD₅₀ of this compound, when orallyingested into human beings, is held to be 1000 mg/kg. The fact that thediethylene glycol the use of which as a food additive was banned in 1985has been incorporated in foreign wines for the purpose of adding to thebody and sweetness of fine and these foreign wines have been imported toour country has been divulged and has become a subject of discussion.

[0162] The adsorbents produced in Example 4 and Control 1 were adoptedand tested for removal by adsorption of diethylene glycol. Diethyleneglycol was dissolved in methanol at a concentration of 100 μg/ml toprepare the solution in an amount of 100 g. Forty (40) g of thissolution and 3 g of a given adsorbent were kept stirred. Liquid layerswere collected meanwhile in a fixed volume of 10 ml at intervals of afixed length along the course of time and subjected to extraction. Theextracts were concentrated at 45° C. and then diluted with added waterto 10 ml and the produced dilute solutions were adopted as testsolutions. These solutions were treated by the method described at pages114-115 of the “Pictorial Guide to Method for Testing Food Hygiene”compiled by Misao Haruta et al. and published by Chuo Hoki Press, withnecessary modifications, and tested by the gas chromatography method fordiethylene glycol concentration.

[0163] The time which elapsed until the diethylene glycol concentrationfell below the limit of detection (10 ppm) was three minutes in the caseof the adsorbent of Example 4, whereas it was ten minutes in the case ofthe adsorbent of Control

EXAMPLE 28

[0164] Test for prevention of hangover (removal by adsorption ofacetaldehyde)

[0165] The adsorbents produced in Example 3 and Control 1 were adoptedand tested for prevention of hangover. Of a panel of 20 adult malemembers, 10 members each ingested 10 g of the adsorbent of Example 3 and10 members each ingested 10 g of the adsorbent of Control 1 immediatelybefore they began drinking an average of 500 ml of alcohol beverage(Japanese sake having an alcohol content of 16%) per head over a periodof two hours.

[0166] When the physical conditions of the panel members were visuallyexamined individually after 12 hours of drinking the alcohol beverage,none of the ten members of the group which took the adsorbent of Example3 before the drinking either felt nausea or felt sick, whereas six ofthe 10 members of the group which took the adsorbent of Control 1 beforethe drinking felt sick and none of them felt nausea or ill.

EXAMPLE 29

[0167] Test for prevention of degradation of oil (removal by adsorptionof hydroperoxide)

[0168] The adsorbents produced in Example 6 and Control 1 were adoptedand tested for prevention of degradation of oil. Five hundred (500) mlof sesame oil was heated to 145-150° C. and deeply fried 50 g of carpfor ten minutes. The oil was cooled to 28±1° C. and then heated again to145-150° C. The deep frying of carp with the same oil was performed upto ten repetitions. Ten (10) g of a given adsorbent was placed in acovered stainless steel basket, placed in the used oil, and rated foroffensive odor, color, foaming property, viscosity, separation of oil,and smoke (230-240° C.) in comparison with the adsorbent in an unusedoil to determine the degree of degradation of the oil.

[0169] The time which elapsed until the assumption of the degradation bythe used oil completely ceased to exist as compared with the unused oilwas ten minutes in the case of the adsorbent of Example 6, whereas itwas 30 minutes in the case of the adsorbent of Control 1.

EXAMPLE 30

[0170] Test for deodorization of old rice (removal by adsorption ofcarbonyl compound)

[0171] It is said that when old rice is boiled and stored at a hightemperature in high humidity, it induces decomposition of fatty acids,forms such carbonyl compounds as n-valeoaldehyde and n-caproaldehyde,and assumes the odor peculiar to old rice.

[0172] The adsorbents produced in Example 3 and Control 2 were eachmolded in the form of spheres (about 2 cm in diameter) and tested fordeodorization of old rice. Boiled rice was obtained by washing 540 g ofthe old rice with water, placing the washed rice in an automatic ricecooker, immersing a given adsorbent in the washed rice, dipping the ricein water of an adjusted amount, and boiling the rice.

[0173] The number of adsorbent spheres required for thorough removal ofthe odor of old rice was one in the case of the adsorbent of Example 3,whereas it was three in the case of the adsorbent of Control 1.

EXAMPLE 31

[0174] Test for removal by adsorption of E. coli BEROTOKISHIN

[0175] The adsorbent produced in Example 4 was adopted and tested forremoval by adsorption of the toxin (BEROTOKISHIN types 1 and 2) producedby the strain 0157 of the pathogenic E. coli. The reagent, culturemedium, and E. coli used in the test were as follows. Reagent: E. coliBEROTOKISHIN detection kit (made by Denka Seiken K.K.) CA-YE culturemedium: Casamino acid 20 g Yeast extract 6 g NaCl 2.5 g K₂HPO₄ 8.71 gSalt solution* 1 ml Distilled water 1000 ml pH 8.5 (1 N NaOH used)Composition of salt solution MgSO₄   5% MnCl₂ 0.5% FeCl₃ 0.5% Thereagent was dissolved in 0.001 N H₂SO₄. LB culture medium Bactotrypton10 g Yeast extract 5 g NaCl 5 g Distilled water 1000 ml pH 7.2 (1 N NaOHused) E. coli TT-11 (microbe offered by National Infant Medical Center)

[0176] In sterilized test tubes, the CA-YE culture medium was dispensedin a fixed volume of 10 ml and the microbe was inoculated to the culturemedium by the use of a platinum wire and the culture medium wasvigorously shaken (120 cycles/min.) for culture at 37° C. for 18 hours.The culture broth was centrifuged at 4° C. at 3500 rpm for 20 minutesand subjected to filtration sterilization by the use of 0.45 μm ofAcrodisc. The filtrate was dispensed in tubes in a fixed volume of 2 mland then mixed for ten minutes with a given adsorbent added thereto in aprescribed amount and subsequently left standing at rest at 4° C. for 24hours. The mixed solutions were centrifuged at 4° C. at 3000 rpm for 20minutes and then filtered with 0.45 μm of Acrodics. The filtratesconsequently obtained were adopted as test solutions.

[0177] To each of the test solutions, a diluent was added dropwise in afixed volume of 25 μl in a total of eight wells in three rows of amicroplate (U type) with the aid of a dropper. For the control ofBEROTOKISHIN, the diluent was added dropwise in a fixed volume of 25 μlin a total of eight wells two rows with the aid of a dropper. The testsolutions excepting those in the final well (the final well using latexas control) were diluted to two degrees. Similarly, the controlBEROTOKISHIN Type 1 and type 2 were respectively diluted in two degreesper row. A sensitized latex VT1 was added dropwise to the first row ofthe diluted series of test solution, a sensitized latex VT12 to thesecond row thereof, and a control latex to the third row thereofrespectively in a fixed volume of 25 μl. The sensitized latex VT1 wasadded dropwise to the diluted series of the control BEROTOKISHIN type 1and sensitized latex VT2 to the diluted series of the controlBEROTOKISHIN type 2 respectively in a fixed volume of 25 μl. Themicroplate was thoroughly shaken to ensure intimate mixture of the testsolutions and the latex reagents. The microplate was covered to precludevaporization of the reaction solutions, left standing at rest at roomtemperature for not less than 20 hours, and then mounted on a blacksheet of paper spread on a bright flat place. The images of latexsediments in the individual wells of the plate were observed with anunaided eye by way of evaluation of qualities. The results of theremoval by adsorption of the BEROTOKISHIN type 1 and type 2 are shownrespectively in Table 2 and Table 3.

[0178] Table 2

[0179] Visual observation of images of latex precipitates in wells

[0180] Table 3

EXAMPLE 32

[0181] Test for preventing diarrhea caused by oral ingestion ofantibiotic substance (Erythromycin)

[0182] To a group of six rabbits, 3.0-3.2 kg in body weight,Erythromycin was orally ingested 12 times at intervals of 6 hours in afixed amount of 40 mg per head each time by the use of fixed feed. Theadsorbent produced in Example 6 was orally ingested to the rabbits in afixed amount of 3 g per head 30 minutes prior to each round of theingestion.

[0183] The symptom of diarrhea was manifested in 100% of the rabbits ofthe group not using the adsorbent and 0% of the rabbits of the groupusing the adsorbent. At this time, in the group of rabbits taking theadsorbent and the group of rabbits not taking the adsorbent alike, theconcentration of Erythromycin in the blood measured 1.5 hours after theoral ingestion was invariably in the range of 0.12-0.13 μg/ml.

EXAMPLE 33

[0184] Test for prevention of diarrhea caused by oral ingestion ofantibiotic substance (Erythromycin)

[0185] A male, 60 years in age and 78 kg in body weight, was made to eatmeals at intervals of six hours and take orally 300 mg of Erythromycin 5minutes after each meal. The symptom of diarrhea manifested itself onthe 18th oral ingestion. Then, the oral ingestion was discontinued.

[0186] The same male was made to take ordinary meals for one month afterthe recovery from the diarrhea and then take orally Erythromycin in thesame manner as above and also take orally 10 g of the adsorbent producedin Example 2 30 minutes prior to each of the meals. No symptom ofdiarrhea manifested itself even on the 20th oral ingestion.

EXAMPLE 34

[0187] Production of adsorbent-containing agar

[0188] In one liter of a boiling decoct of dried bonito, 100 g of theadsorbent produced in Control 1 was boiled for three minutes. A 10-gsample of the produced soup was placed in an aluminum container, 30 cm³in inner volume, and was thoroughly mixed with 15 g of an agar solutionadded thereto. The resultant mixture was deaerated, then hot sealed witha lid of aluminum foil, and sterilized in an autoclave at 121° C. for 20minutes to obtain an adsorbent-containing agar.

EXAMPLE 35

[0189] Production of adsorbent-containing agar

[0190] An adsorbent-containing agar was obtained by following theprocedure of Example 31 while using the adsorbent produced in Control 3instead.

EXAMPLE 36

[0191] Production of adsorbent-containing agar

[0192] In an aluminum container, about 50 cm³ in inner volume, 10 g ofthe adsorbent-containing agar produced by following the procedure ofExample 31 was placed and 20 g of an agar solution was added thereto. Onthe resultant mixture, a kelp seasoned with salad oil of Chinese fashionwas superposed and 10 g of the agar solution was further added thereon.The resultant mixture was deaerated and, with the container heat sealedwith a lid of aluminum foil, sterilized in an autoclave at 121° C. for20 minutes to obtain an adsorbent-containing agar.

EXAMPLE 37

[0193] Production of adsorbent-containing calcium alginate gel

[0194] An adsorbent-containing calcium alginate gel was obtained byfollowing the procedure of Example 31 while using the adsorbent producedin Example 3 instead and using calcium alginate gel in the same amountinstead of the agar solution.

EXAMPLE 38

[0195] Production of adsorbent-containing calcium alginate gel

[0196] An adsorbent-containing calcium alginate gel was obtained byfollowing the procedure of Example 34 while using the adsorbent producedin Example 9 instead.

EXAMPLE 39

[0197] Production of adsorbent-containing calcium alginate gel

[0198] An adsorbent-containing calcium alginate gel was obtained byfollowing the procedure of Example 33 while using the adsorbent producedin Example 4 instead and using calcium alginate gel in the place of theagar solution.

[0199] Industrial Applicability

[0200] The adsorbent of this invention is obtained by coating anadsorption basis with a gel-like substance and then subjecting thecoated absorption basis to a freezing treatment and is formed of adispersed system having the adsorption basis uniformly dispersed in thegel-like substance and, therefore, is capable of effecting removal byadsorption of a harmful substance with unusually high efficiency withoutsacrificing the adsorbing ability which is inherent in the adsorptionbasis.

[0201] The adsorbent of this invention can manifest the same effect asmentioned above because it is obtained by coating an adsorption basiswith a gel-like substance already containing a frost harm preventingsubstance and subsequently depriving the coated adsorption basis of thefront harm preventing substance.

[0202] Further, the adsorbent of this invention, when adopting minuteparticles of powdered active carbon, for example, as the adsorptionbasis, is allowed to form a dispersed system having the adsorption basisuniformly dispersed in a gel-like substance. It is, therefore, capableof effecting removal by adsorption of a harmful substance with unusuallyhigh efficiency because the adsorbent as a whole enjoys an increasedarea available for adsorption and a consequent increase in the abilityto effect adsorption as compared with the active carbon which is usedall by itself owing to the addition to the efficiency of dispersion ofactive carbon.

[0203] Since the adsorbent of this invention has an adsorption basiscoated with a gel-like substance, it can be directly ingested into thedigestive system and can easily effect removal by adsorption of theharmful substance introduced as mixed with a foodstuff into thedigestive system. Moreover, this adsorbent avoids inducing such atrouble as constipation even when it is directly ingested into thedigestive system. The adsorbent which has effected the removal byadsorption of the harmful substance in the digestive system can be veryquickly and easily discharged from the digestive system.

[0204] The adsorbent of this invention can be made to effect the removalby adsorption of the harmful substance contained in a foodstuff by beingbrought into direct contact with the foodstuff. In this case, theadsorbent which has effected the removal by adsorption of the harmfulsubstance can be separated easily and quickly from the foodstuff ascompared with the adsorbent which is used all by itself. Even when theadsorbent erroneously mingles into a foodstuff and ultimately reachesthe interior of the digestive system without being separated, it is safeall the same because it is quickly discharged from the digestive systemas described above.

[0205] The adsorbent of this invention, besides being utilized fordirect ingestion into the digestive system as described above, can beutilized as mixed with a processed foodstuff, for example. When theadsorbent of this invention is fixed with a processed foodstuff and theresultant mixture is eaten, it avoids imparting a sensation of thepresence of foreign matter, excels in palatability, and precludes thepossibility of tainting the foodstuff in black tint.

[0206] Since the adsorbent of this invention manifests the outstandingeffect mentioned above, it is particularly useful for the removal byadsorption of such food additive, feed additive, agricultural pesticide,food poisoning substance, allergen, heavy metal or highly poisonousorganic compound as are suffered to adhere to or exist in thefoodstuffs, such surplus nutrients as persist in the digestive system,such oligomers and additives as are contained in liquors, suchmetabolites of alcohol as are formed in the digestive system afterassimilation of alcohol, such harmful substances as hydroperoxides ofunsaturated fatty acids as are suffered to exist in oils and fats, andsuch components of offensive odor as emanate from fish.

1. An adsorbent formed by coating an adsorption basis with a gel-likesubstance and subsequently subjecting the coated basis to a freezingtreatment.
 2. An adsorbent formed by coating an adsorption basis with agel-like substance already containing a frost damage preventingsubstance and subsequently depriving the coated basis partly or whollyof said frost damage preventing substance.
 3. An adsorbent according toclaim 2, wherein said frost damage preventing substance is glycerin. 4.An adsorbent according to any of claims 1-3, wherein said adsorptionbasis is a carbonaceous material possessing the ability to effectadsorption.
 5. An adsorbent according to claim 4, wherein saidcarbonaceous material possessing the ability to effect adsorption isactive carbon or charcoal.
 6. An adsorbent according to any of claims1-5, wherein said gel-like substance is the divalent metallic salt of amacromolecular polycarboxylic acid.
 7. An adsorbent according to claim6, wherein said divalent metallic salt of said macromolecularpolycarboxylic acid is calcium alginate.
 8. An adsorbent according toany of claims 1-5, wherein said gel-like substance is soybean curd,jelly, konjak, agar, perilla, gelidium jelly, or chitosanoxalic acidsalt gel.
 9. An adsorbent formed by drying an adsorbent set forth in anyof claims 1-8.
 10. An adsorbent comprising an adsorbent moiety formed bycoating an adsorption basis with a first gel-like substance and a secondgel-like substance moiety.
 11. An adsorbent according to claim 10, whichis formed by seasoning either said adsorbent moiety or said secondgel-like substance moiety.
 12. An adsorbent according to claim 10 orclaim 11, wherein said adsorbent moiety comprises an adsorbent set forthin any of claims 1-9.
 13. An agent for removal by adsorption of aharmful substance, which comprises an adsorbent set forth in any ofclaims 1-12.
 14. An agent according to claim 13, wherein said harmfulsubstance is a food additive, a feed additive, an agriculturalpesticide, a food poisoning substance, allergen, a heavy metal, or astrongly poisonous organic compound which is suffered to adhere to ormingle in a foodstuff or an animal feed or assimilated into thedigestive system.
 15. An agent according to claim 14, wherein said feedadditive is an antibiotic substance, a synthetic antibacterial agent, ora hormone agent.
 16. An agent according to claim 14, wherein said foodpoisoning substance is exotoxins, autotoxins, or a harmful chemicalsubstance.
 17. An agent according to claim 13, wherein said harmfulsubstance is formed of an antibiotic substance which has eitherundergone oral ingestion or acted on the intestinal bacteria.
 18. Anagent for the removal by adsorption of a surplus nutrient assimilated inthe digestive system, which agent comprises an adsorbent set forth inany of claims 1-12.
 19. An agent for the removal by adsorption of theintermediate metabolite of alcohol formed in the digestive system inconsequence of the assimilation of said alcohol, which agent comprisesan adsorbent set forth in any of claims 1-12.
 20. An agent for theremoval by adsorption of hydroperoxide of an unsaturated fatty acid inoil or fat, which agent comprises an adsorbent set forth in any ofclaims 1-23.
 21. A deodorant comprising an adsorbent set forth in any ofclaims 1-12.
 22. A process foodstuff or animal feed incorporatingtherein 0.01-60 wt. % of an adsorbent set forth in any of claims 1-12.23. A processed foodstuff according to claim 22, which is a dairyproduct, a product of fish paste, a processed fish or shellfish, aprocessed meat, processed beans, processed vegetables, a processedpotato, a processed cereal, a sweetener, oil and fat, or a cake.